PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown between the French league champions and the Coupe de France winners after the French winger found the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty win.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
